CN100383175C - Preparation method of thermoplastic polyimide film - Google Patents
Preparation method of thermoplastic polyimide film Download PDFInfo
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- CN100383175C CN100383175C CNB2006100281551A CN200610028155A CN100383175C CN 100383175 C CN100383175 C CN 100383175C CN B2006100281551 A CNB2006100281551 A CN B2006100281551A CN 200610028155 A CN200610028155 A CN 200610028155A CN 100383175 C CN100383175 C CN 100383175C
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Abstract
The present invention relates to a preparation method of a thermoplastic polyimide film, which comprises the following specific steps: bis [4-(3-aminophenoxy) phenyl] sulfone BAPS-m is dissolved in a dimethyl acetamide solution, and the mass percent concentration of the solution is from 15 to 25%; under the condition of cooling the solution by an ice water bath, acid anhydride is added into the solution according to the molar ratio of one to one; the solution is stirred to react for four to five hours at the temperature below 0 to 30 DEG C, and then, polyamic acid is prepared; the polyamic acid which is obtained in the step a is coated on a flat plate mould, and after the mould is heated by a program to carry out hot thermoplastic polyimide react, the mould is slowly cooled to obtain the thermoplastic polyimide film; the mould is heated by the program for one hour respectively at the temperature of 80 DEG C, 120 DEG C, 160 DEG C, 200 DEG C, 250 DEG C and 300 DEG C. The thermoplastic polyimide film which is prepared by the method of the present invention can be used as a hot melting bonding transition layer to replace a traditional epoxy bonding layer; when the thermoplastic polyimide film is used for manufacturing a flexible circuit board, compared with a traditional flexible circuit board, the flexible circuit board which is manufactured by the thermoplastic polyimide film has good thermal stability.
Description
Technical field
The present invention relates to a kind of preparation method of thermoplastic polyimide film, particularly a kind of is the preparation method of the thermoplastic polyimide film of diamines raw material with two [4-(3-amino-benzene oxygen) phenyl] sulfone (BAPS-m).
Background technology
Polyimide (polyimide) is called for short PI, refers to contain in the molecular chain imine structure
A family macromolecule compound.Owing to have very stable fragrant heterocycle structure unit in the PI molecule, make its excellent heat resistance performance, can be under 250 ℃ environment life-time service, and keep its every performance not change substantially.The tensile strength of the excellent PI of mechanical property, shock strength and modulus are all than higher, and wear resistance and antifriction quality are also better.And the high-temperature mechanical property of material is good.Electrical property is good: the PI electrical insulating property is good, and dipolar loss is little in wide temperature range, and corona resistance is good, and specific inductivity is also lower.Outstanding chemical resistance, organic solvent resistance, winter hardiness, weathering resistance, frictional behaviour, creep resisting ability etc.
When the rigid structure of polyimide is given its premium properties, also cause it to have infusibility, insoluble.Therefore its moulding processability is poor.The polyimide poor processability has become the maximum restraining factors that the resin that hinders this excellent performance is used widely.To be the user one of require the maximum of polyimide the processing characteristics of improving polyimide,
The inferior PI film of polyamides is mainly used in electric, electronic applications.Increasing the most traditional flexible print circuit board with flexible print circuit board (FPC) again in recent years is base material PI/ tackiness agent/Copper Foil three-decker.Because Kapton does not have thermoplasticity, has to by means of tackiness agent, using maximum tackiness agent is Resins, epoxy.This makes the thermotolerance of product be subjected to very big influence.In order to address these problems, can adopt following three kinds of modes: the first prepares a kind of thermoplastic polyimide film, directly and Copper Foil compound.Because Copper Foil is oxidation easily at high temperature, its highest combined temp should not surpass 300 ℃, and therefore the Kapton that can satisfy the demands must have certain thermoplastic viscosifying power below 300 ℃, requires to possess thermotolerance and low linear expansivity simultaneously again.Regrettably still can't find the polyimide material that satisfies this condition so far; It two is that the presoma polyamic acid is coated on the Copper Foil, hot imidization again, but this technology can't adapt to the manufacture process requirement of flexible circuit board; The third method is a kind of thermoplastic polyimide film of preparation, as the hot melting cohesion transition layer, substitute traditional epoxy bonds layer, still be traditional flexible circuit board three-decker, do not change the flexible circuitry board production technology, but improved the resistance toheat of flexible circuit board greatly.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of thermoplastic polyimide film, particularly a kind of is the diamines raw material with two [4-(3-amino-benzene oxygen) phenyl] sulfone (BAPS-m), synthetic method with thermoplastic polyimide film of thermo-compression bonding characteristic.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of thermoplastic polyimide film is characterized in that it is the diamines raw material that this method adopts two [4-(3-amino-benzene oxygen) phenyl] sulfone BAPS-m, and concrete steps are as follows:
A) two [4-(3-amino-benzene oxygen) phenyl] sulfone BAPS-m are dissolved in the dimethylacetamide solution, its mass percent concentration is 15～25%; Under the ice-water bath cooling,, add dicarboxylic anhydride with 1: 1 mol ratio; Then under 0～30 ℃, stirring reaction 4～5 hours, preparation polyamic acid;
B) step a is obtained polyamic acid and coat on the flat plate mold, through the temperature programming hot imidization, slowly cooling promptly obtains thermoplastic polyimide film; The temperature and time of temperature programming is: 80 ℃, 120 ℃, 160 ℃, 200 ℃, 250 ℃, 300 ℃ each one hour.
Above-mentioned dicarboxylic anhydride is: pyromellitic acid acid anhydride PMDA or 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride BTDA or 3,3 ', 4,4 '-biphenyl tetracarboxylic acid anhydrides BPDA or 4,4 '-oxidation dibenzoic acid acid anhydride OPDA.
Compared with prior art, the inventive method has following outstanding substantive distinguishing features and remarkable advantage: the thermoplastic polyimide film that to adopt two [4-(3-amino-benzene oxygen) phenyl] sulfone BAPS-m be the diamines feedstock production has the thermoplastic processability, under certain temperature and pressure can with Copper Foil and other non-thermal plasticity Kapton compoiste adherings.Can be used as the hot melting cohesion transition layer, substitute traditional epoxy bonds layer, be used for the prepared flexible circuit board of flexible circuit board and have better thermostability with respect to traditional flexible circuit board.。
Concrete embodiment:
Embodiment one: add 12.96g (0.03mol) BAPP and 80mlDMAc in the special-purpose big mouthful reactor of exsiccant, be stirred to BAPP under the room temperature and dissolve fully.The ice-water bath cooling adds PMDA6.54g (0.03mol) (amine: acid anhydride=1: 1) down.Stirring reaction is five hours under the room temperature, makes polyamic acid solution.
With coating device polyamic acid solution is evenly coated on the flat plate mold that acetone cleans up, coating thickness is at the 15-25 micron.
The flat plate mold level that scribbles polyamic acid solution is put into baking oven, at 80 ℃, 120 ℃, 160 ℃, 200 ℃, 250 ℃, respectively kept one hour under 300 ℃, close the baking oven power supply, make it in baking oven, naturally cool to room temperature, take out flat plate mold and immerse demoulding in the water, obtain Kapton, dry naturally.
The second-order transition temperature of this film is 308.16 ℃, and 5% thermal weight loss temperature is 529.97 ℃, and 10% thermal weight loss temperature is 559.46 ℃, and linear expansivity is 61.56ppm/ ℃, tensile strength 81.7Mpa, elongation at break 5.2%.
Embodiment two: add 12.96g (0.03mol) BAPP and 80mlDMAC in the special-purpose big mouthful reactor of exsiccant, be stirred to BAPP under the room temperature and dissolve fully.The ice-water bath cooling adds BPDA8.82g (0.03mol) (amine: acid anhydride=1: 1) down.Stirring reaction is five hours under the room temperature, makes polyamic acid solution.
With coating device polyamic acid solution is evenly coated on the flat plate mold that acetone cleans up, coating thickness is at the 15-25 micron.
The flat plate mold level that scribbles polyamic acid solution is put into baking oven, at 80 ℃, 120 ℃, 160 ℃, 200 ℃, 250 ℃, respectively kept one hour under 300 ℃, close the baking oven power supply, make it in baking oven, naturally cool to room temperature, take out the sheet glass mould and immerse demoulding in the water, obtain Kapton, dry naturally.
The second-order transition temperature of this film is 247.73 ℃, and 5% thermal weight loss temperature is 541.66 ℃, and 10% thermal weight loss temperature is 561.57 ℃, and linear expansivity is 51.56ppm/ ℃, and tensile strength is 113Mpa, and elongation at break is 7.0%.
Claims (2)
1. the preparation method of a thermoplastic polyimide film is characterized in that it is the diamines raw material that this method adopts two [4-(3-amino-benzene oxygen) phenyl] sulfones, and concrete steps are as follows:
A, two [4-(3-amino-benzene oxygen) phenyl] sulfones of general are dissolved in the dimethylacetamide solution, and its mass percent concentration is 15～25%; Under the ice-water bath cooling,, add dicarboxylic anhydride with 1: 1 mol ratio; Then under 0～30 ℃, stirring reaction 4～5 hours, preparation polyamic acid;
B, step a is obtained polyamic acid coat on the flat plate mold, through the temperature programming hot imidization, slowly cooling promptly obtains thermoplastic polyimide film; The temperature and time of temperature programming is: 80 ℃, 120 ℃, 160 ℃, 200 ℃, 250 ℃, 300 ℃ each one hour.
2. the preparation method of thermoplastic polyimide film according to claim 1 is characterized in that, above-mentioned dicarboxylic anhydride is: pyromellitic acid acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic acid anhydrides or 4,4 '-oxidation dibenzoic acid acid anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100281551A CN100383175C (en) | 2006-06-27 | 2006-06-27 | Preparation method of thermoplastic polyimide film |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100281551A CN100383175C (en) | 2006-06-27 | 2006-06-27 | Preparation method of thermoplastic polyimide film |
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| CN1869103A CN1869103A (en) | 2006-11-29 |
| CN100383175C true CN100383175C (en) | 2008-04-23 |
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| CNB2006100281551A Expired - Fee Related CN100383175C (en) | 2006-06-27 | 2006-06-27 | Preparation method of thermoplastic polyimide film |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993748B (en) * | 2012-10-19 | 2014-10-08 | 南京理工大学 | Polyimide film and method for preparing double-layer flexible copper-clad plate by utilizing same |
| CN110117010B (en) * | 2019-06-10 | 2024-04-05 | 浙江华炜新材料有限公司 | Polyimide film fixing die for producing graphite heat conducting film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089357C (en) * | 1994-03-31 | 2002-08-21 | 住友电木株式会社 | Polyimidesiloxane adhesive |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089357C (en) * | 1994-03-31 | 2002-08-21 | 住友电木株式会社 | Polyimidesiloxane adhesive |
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| CN1869103A (en) | 2006-11-29 |
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Granted publication date: 20080423 Termination date: 20110627 |